Donor-stabilized five-coordinate cationic chelate silicon compounds with two (O→Si)-coordinating ligands

Taylor, Peter and Bassindale, Alan (2011). Donor-stabilized five-coordinate cationic chelate silicon compounds with two (O→Si)-coordinating ligands. Russian Journal of General Chemistry, 81(12) pp. 2412–2427.

DOI: https://doi.org/10.1134/S1070363211120036

Abstract

Cationic O→Si-coordinated bis-C,O-chelate silicon complexes [(LCH₂)₂Si(F)]BF₄, containing monoanionic AcN(Me)CH₂, 2-oxoperhydroazepinomethyl, 2,2-dimethyl-4-oxobenzo[1,3]oxazin-3-ylmethyl, and 4-methyl-2-oxoquinolinomethyl C,O-coordinating ligands were synthesized by the reaction of trimethylsilyl derivatives of amides, lactams, and related compounds with (ClCH₂)₂SiC1₂ in a 2:1 ratio. The synthesized complexes were reacted with KF to obtain six-coordinate bis-C,O-chelates [(LCH₂)₂SiF₂] which were then converted into the starting tetrafluoroborates by treatment with BF₃•Et₂O. First representatives of cationic bis-O,O'-chelate silicon complexes with a 2-hydroxyacid amide fragment {XSi[OCH(R)C(O)NMe₂]₂}Y (X = C1, Me, t-Bu, Ph, BrCH₂; R = H, Me; Y - Cl^-, C1HC1^-, HgBr ₃ ^- ) were synthesized by the reaction of XSiC1₃ with O→SiMe₃ derivatives of dimethylamides of (S)-lactic and glycolic acids in a 1:2 ratio or by transesterification of XSi(OMe)₃ with glycolic acid dimethylamide followed by addition of acetyl bromide (ratio 1:3:1). The structure of the resulting chelates was proved by X-ray diffraction analysis.

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